Reactive polyurethane dispersions

ABSTRACT

The present disclosure is drawn to reactive polyurethane dispersions. In one example, a reactive polyurethane dispersion can include a polymer strand having a polymer backbone that has two ends terminating at a first capping unit and a second capping unit. The polymer backbone can include polymerized monomers including a reactive diol and a diisocyanate. The reactive diol can be an acrylate-containing diol, a methacrylate-containing diol, an acrylamide-containing diol, a methacrylamide-containing diol, or combination thereof. The first capping unit can be an acrylamide-containing monoalcohol or methacrylamide-containing monoalcohol reacted with an isocyanate group of the diisocyanate. The second capping unit can be an ionic stabilizing group.

BACKGROUND

Radiation curable compositions, such as ultraviolet (UV) curablecompositions, can become highly durable solids upon curing. UV-curablepolyurethane, for example, has been used in applications such as paints,floor finishes, aircraft coatings, industrial coatings, and so on.UV-curable polyurethane coatings can be applied in liquid form and thencured very quickly using UV radiation to produce a hard, durablecross-linked coating.

BRIEF DESCRIPTION OF THE DRAWINGS

Additional features and advantages of the disclosure will be apparentfrom the detailed description which follows, taken in conjunction withthe accompanying drawings, which together illustrate, by way of example,features of the present technology.

FIG. 1 is an example reaction scheme showing a reaction pathway forforming a polymer strand of a reactive polyurethane dispersion inaccordance with the present disclosure; and

FIG. 2 is a flowchart of an example method of making a reactivepolyurethane dispersion in accordance with the present disclosure.

Reference will now be made to several examples that are illustratedherein, and specific language will be used herein to describe the same.It will nevertheless be understood that no limitation of the scope ofthe disclosure is thereby intended.

DETAILED DESCRIPTION

The present disclosure is drawn to reactive polyurethane dispersions.These reactive polyurethane dispersions can be used in UV-curablewater-based inkjet inks. Generally, UV-curable inkjet inks can includewater, a colorant, a photoinitiator, and a reactive component such asmonomers or reactive polymers that can polymerize or cross-link uponexposure to UV radiation. The polyurethane dispersions described hereincan include reactive groups such as acrylate, methacrylate, acrylamideand methacrylamide groups that can cross-link the polyurethane when theUV-curable ink is exposed to UV radiation.

In further detail, the reactive polyurethane dispersions describedherein can include polymer strands with acrylamide or methacrylamidereactive groups in capping units at the ends of the strands. In someexamples, a reactive polyurethane dispersion can include a polymerstrand that has a polymer backbone having two ends terminating at afirst capping unit and a second capping unit. The polymer backbone canbe formed of polymerized monomers including: a reactive diol selectedfrom an acrylate-containing diol, a methacrylate-containing diol, anacrylamide-containing diol, a methacrylamide-containing diol, orcombination thereof; and a diisocyanate. The first capping unit can bean acrylamide-containing or methacrylamide-containing monoalcoholreacted with an isocyanate group of the diisocyanate. The second cappingunit can be an ionic stabilizing group. In one example, the polymerbackbone can be devoid of ionic stabilizing groups. In another example,the reactive polyurethane dispersion can have an NCO/OH ratio of 1.2 to10, an acid number of 20 to 100, and/or a double bond density of 1.5 to10. In further detail, the reactive polyurethane dispersion can bedevoid of polymer strands having capping units that include acrylategroups or methacrylate groups. In still other examples, a majority ofpolymer strands in the reactive polyurethane dispersion can have a firstcapping unit that is an acrylamide-containing monoalcohol ormethacrylamide-containing monoalcohol reacted with an isocyanate groupof the diisocyanate and a second capping unit that is an ionicstabilizing group.

The reactive polyurethane dispersion can be used in a UV-curable inkcomposition as well. The UV-curable ink composition can include acolorant, a photoinitiator, and a reactive polyurethane dispersion. Thereactive polyurethane dispersion can include a polymer strand that has apolymer backbone having two ends terminating at a first capping unit anda second capping unit. The polymer backbone can be formed of polymerizedmonomers including: a reactive diol selected from an acrylate-containingdiol, a methacrylate-containing diol, an acrylamide-containing diol, amethacrylamide-containing diol, or combination thereof; and adiisocyanate. The first capping unit can be an acrylamide-containing ormethacrylamide-containing monoalcohol reacted with an isocyanate groupof the diisocyanate. The second capping unit can be an ionic stabilizinggroup. In one specific example, the UV-curable ink composition can havea pH of 7.0 to 11.5, and/or the pH does not decrease by more than 1.0when the UV-curable ink composition is exposed to accelerated shelf-life(ASL) at 50° C. in open air for 1 week. In other examples, the polymerbackbone can be devoid of ionic stabilizing groups.

In a further example, a method of making a reactive polyurethanedispersion can include reacting a diisocyanate with a reactive diolselected from an acrylate-containing diol, a methacrylate-containingdiol, an acrylamide-containing diol, a methacrylamide-containing diol,or combination thereof, to form a first pre-polymer. The firstpre-polymer can be reacted with an acrylamide-containing ormethacrylamide-containing monoalcohol to form a second pre-polymer. Thesecond pre-polymer can then be reacted with an acid-containing amine toform a polymer strand. The polymer strand can be dispersed in water toform the reactive polyurethane dispersion. In one example, the methodcan include adding a colorant and a photoinitiator to the reactivepolyurethane dispersion to form a UV-curable ink composition.

The reactive polyurethane dispersions described herein can be pH-stablein inkjet ink compositions. Inkjet inks are often basic, having a pH inthe range of about 7.0 to about 11.5. Acrylate monomers are often usedin reactive polyurethanes, but the acrylate groups are easily hydrolyzedunder the basic conditions of inkjet ink. This results in a drop in thepH of the ink over time. The drop in pH of the inkjet can result inproblems with the ink, such as causing dispersed pigments to crash outof dispersion making the ink unjettable. The reactive polyurethanedispersions described herein can overcome these challenges because thereactive polyurethane dispersions can have a stable pH over time, whilealso being curable by UV radiation to provide a durable printed image.

As used herein, “pH-stable” means a composition that changes less than 1pH unit after two weeks in accelerated shelf-life (ASL) conditions. ASLrefers to an experimental test designed to test the shelf-life of acomposition in an accelerated time frame. ASL tests referred to hereinare performed by placing a composition in a container open to air at atemperature of 50° C. It is assumed that each week under theseconditions simulates six months of shelf-life time under normal storageconditions.

Many commercially available reactive pH dispersions are intended forUV-curable coating applications. Commercially available reactive pHdispersions include dispersions sold under the names Ucecoat®6558,Ucecoat@6559, Ebecryl®2002 and Ebecryl®2003 (available from Cytec).Other representative acrylated CPUDs include Ucecoat®7710, Ucecoat®7655(available from Cytec), Neorad®R440, Neorad®R441, Neorad®R447,Neorad®R448 (available from DSM NeoResins), Bayhydrol®UV 2317,Bayhydrol®UV VP LS 2348 (available from Bayer), Lux®430, Lux®399,Lux®484 (available from Alberdingk Boley), Laromer®LR8949,Laromer®LR8983, Laromer®PE22WN, Laromer®PE55WN, Laromer®UA9060(available from BASF). Under basic aqueous conditions, thesecommercially available dispersions hydrolyze easily and produce morethan one or two units of pH drop after 1 week ASL.

The reactive polyurethane dispersions described herein includeparticular combinations of functional groups in the polymer backbone andcapping units of the polyurethane polymer strands in the dispersions.These combinations of functional groups and their placement in thepolymer strands can improve the pH-stability of the dispersions. Thus,the present reactive polyurethane dispersions can overcome thepH-stability limitations of commercially available polyurethanedispersions when used in basic aqueous inks. In some examples, thepresent reactive polyurethane dispersions do not exhibit the large pHdrop under basic aqueous conditions that occurs with the commerciallyavailable polyurethane dispersions mentioned above.

To clarify the structure of polymer strands in the reactive polyurethanedispersion, Formula (I) shows one example of a general chemicalstructure of a polymer strand in the polyurethane dispersion:

In Formula (I), R₁, R₂, R₃, R₄, and R₅ can correspond to the followinggroups: R₁ can be an organic group that includes an acrylamide ormethacrylamide functional group; R₂ can be an organic group; R₃ can bean organic group containing an acrylate, methacrylate, acrylamide, ormethacrylamide functional group; R₄ can be an ionic stabilizing group;and R₅ can be hydrogen or an additional organic group. The term “organicgroup” can generally refer to carbon-containing groups with from 1 to 20carbon atoms, and can be straight chained, branched, alicyclic,aromatic, etc. Organic groups can be substituted with O, S, P, N, B,etc. Additionally, n can be any integer, for example from 1 to 1,000.The polymer strand includes capping units that include groups R₁, R₄,and R₅ with a polymer backbone between the capping units. As is commonwith polyurethane polymers, in some examples the polymer backbone can beformed by polymerizing a diisocyanate and a diol. The polymer backboneshown in Formula (I) can be formed by reacting a diisocyanate havingFormula (II) with a diol having Formula (III):O═C═N—R₂—N═C═O  (II)HO—R₃—OH  (III)

The diisocyanate and diol can polymerize to form a polymer backbone ofalternating polymerized diisocyanate and diol groups. The capping unitscan be added at each end of the polymer backbone by introducing amonofunctional monomer that includes the groups R₁ or R₄ and R₅. Invarious examples, the monofunctional monomer can be a monoalcohol ormonoamine that reacts with the unreacted isocyanate groups of thediisocyanate monomers at the ends of the polymer backbone. In certainexamples, the polymer strand can include different capping units at eachend of the polymer strand. This is shown in Formula (I). However, inother examples, the polymer strand can have two identical capping units.

In some examples, the polymer strands of the reactive polyurethanedispersion can include a polymer backbone including polymerizedmonomers. The polymerized monomers in the polymer backbone can include areactive diol and a diisocyanate. In certain examples, the reactive diolcan be selected from an acrylate-containing diol, amethacrylate-containing diol, an acrylamide-containing diol, amethacrylamide-containing diol, or combination thereof. As used herein,“acrylate-containing diol” refers to a chemical compound that has twohydroxyl groups and an acrylate functional group. Similarly,“methacrylate-containing diols,” “acrylamide-containing diols,” and“methacrylamide-containing diols” refer to diol compounds that includemethacrylate, acrylamide, and methacrylamide functional groups,respectively.

These reactive diols can polymerize with the diisocyanate to form thepolymer backbone. In the polymerizing process, an oxygen atom in ahydroxyl group of the reactive diol forms a bond with a carbon atom inan isocyanate group of the diisocyanate. This is commonly referred to asa urethane linkage. By this process, a polymer backbone forms as a chainof alternating polymerized diisocyanate and reactive diol monomers. Asused herein, “polymerized monomer” is used to describe monomers in theirpolymerized state, e.g., after the monomers have bonded together to forma polymer chain. The names of monomers in their original state may beused even though it is understood that the monomers change in certainways during polymerizing. For example, “polymerized diisocyanate andreactive diol” can refer to a polymer chain formed by polymerizing adiisocyanate and a reactive diol, even though the diisocyanate andreactive diol do not actually exist as separate molecules in thepolymer. In the case of polymerized diisocyanates and reactive diols, ahydrogen atom of the hydroxyl group of the reactive diol is replaced bya bond between the oxygen atom of the hydroxyl group and the carbon atomof the isocyanate group of the diisocyanate. Thus, the reactive diol isno longer a reactive diol, but has become a portion of a polymer chain.However, “polymerized reactive diol” may still be used to refer to thisportion of the polymer chain for the sake of convenience. The portionsof the polymer chain formed from diisocyanates or diols can also bereferred to as “diisocyanate units” and “diol units” for convenience.

Accordingly, in some examples the reactive polyurethane dispersion caninclude a polymer strand having a polymer backbone including polymerizeddiisocyanate and reactive diol. The reactive diol can be anacrylate-containing diol, a methacrylate-containing diol, anacrylamide-containing diol, a methacrylamide-containing diol, orcombination thereof. In examples where multiple types of reactive diolare included, the polymer backbone resulting from polymerizing themonomers can be made up of alternating diisocyanate and diol units,where each of the diol units can be one of the multiple types ofreactive diols that were included in the polymerization reaction. Insome examples, all or substantially all of the diol units in the polymerbackbone can be an acrylate-containing diol, a methacrylate-containingdiol, an acrylamide-containing diol, or a methacrylamide-containingdiol. In alternate examples, a non-reactive diol can also be included inthe polymer backbone. In still further examples, other polyols can beincluded having more than two hydroxyl groups in each polyol molecule.

In certain examples, the reactive diol polymerized in the polymerbackbone can be selected from the following reactive diols:

or a combination thereof.

The reactive diol can include reactive functional groups that canparticipate in UV-curing. Acrylate groups, methacrylate groups,acrylamide groups, and methacrylamide groups can each participate inUV-curing through the double bonds in each of these functional groups.Thus, when the reactive polyurethane dispersion is cured, the doublebonds in the acrylate, methacrylate, acrylamide, and/or methacrylamidegroups can link together to form crosslinking between polymer strands.

The diisocyanate polymerized in the polymer backbone is not particularlylimited. Generally, the diisocyanate is a molecule having two isocyanategroups that can react with the hydroxyl groups of the reactive diol toform urethane linkages. In some examples, the diisocyanate used in thepolymer backbone can be non-reactive. That is, the diisocyanate can bedevoid of reactive functional groups other than the isocyanate groups.For example, the diisocyanate can be devoid of acrylate, methacrylate,acrylamide, methacrylamide, allyl, styrene, and other functional groupsthat can participate in UV-curing. In alternate examples, thediisocyanate can include one or more of such functional groups.

In certain examples, the diisocyanate polymerized in the polymerbackbone can be selected from the following diisocyanates:

or a combination thereof.

Capping units can be added to the polymer backbone by polymerizing amonofunctional monomer with the isocyanate groups at the terminal endsof the polymer backbone. In some examples of the reactive polyurethanedispersion described herein, two distinct capping units can be includedin the polymer strands. In certain examples, a polymer strand can have afirst capping unit at one end of the polymer backbone, and a secondcapping unit at the other end of the polymer backbone. The first cappingunit can be an acrylamide-containing or methacrylamide-containingmonoalcohol reacted with an isocyanate group of the diisocyanate of thepolymer backbone. The second capping unit can be an ionic stabilizinggroup.

As used herein, “ionic stabilizing group” refers to an organic groupthat includes an acidic functional group or other ionic functional groupthat can stabilize the dispersion of the polyurethane in water. Acidicstabilizing groups can include organic acid functional groups (i.e.,carboxyls), sulfonic acid groups, and other acidic functional groups. Insome examples, a capping unit including an ionic stabilizing group canbe an amino acid. In further examples, a capping unit including an ionicstabilizing group can be taurine.

In further examples, the acrylamide-containing ormethacrylamide-containing monoalcohol reacted with an isocyanate groupof the polymer backbone to form the capping unit can be selected fromthe following molecules:

or a combination thereof.

The hydroxyl group of the acrylamide-containing ormethacrylamide-containing monoalcohol can react with the isocyanategroup of the polymer backbone to bond the monoalcohol to the polymerbackbone. The acrylamide or methacrylamide group can be available toparticipate in UV-curing of the polyurethane dispersion.

In some examples, the reactive polyurethane dispersion can include amixture of polymer strands having different combinations of cappinggroups. In particular, some polymer strands may have anacrylamide-containing or methacrylamide-containing monoalcohol bonded tothe polymer backbone at one end, and an ionic stabilizing group bondedto the polymer backbone at the other end. Other polymer strands may havean acrylamide-containing or methacrylamide-containing monoalcohol bondedto both ends of the polymer backbone. Still other polymer strands canhave an ionic stabilizing group bonded to both ends of the polymerbackbone. In one example, the reactive polyurethane dispersion caninclude a majority of polymer strands with an acrylamide-containing ormethacrylamide-containing monoalcohol bonded to one end of the polymerbackbone and an ionic stabilizing group bonded to the other end of thepolymer backbone. These polymer strands can have the advantage ofimproved dispersion stability due to the ionic stabilizing group and theadvantage of the acrylamide or methacrylamide group in the capping unitparticipating in UV-curing to increase the durability of the curedpolyurethane. The reactive polyurethane dispersion can also includesmaller amounts of polymer strands having acrylamide-containing ormethacrylamide-containing capping units at both ends and polymer strandshaving ionic stabilizing groups at both ends. In one example, more than50% of the polymer strands in the reactive polyurethane dispersion canhave the acrylamide-containing or methacrylamide-containing monoalcoholat one end and the ionic stabilizing group at the other end.

In some examples, the reactive polyurethane dispersion can be morepH-stable when particular types of monomers are included or not includedin the polymer backbone and the capping units. In one example, thecapping units in the reactive polyurethane dispersion can be free ofacrylate and methacrylate groups. The capping units can includeacrylamide or methacrylamide groups, as mentioned above. In thisexample, the polymer backbone can include acrylate, methacrylate,acrylamide, and/or methacrylamide groups. In another example, thepolymer backbone can be free of ionic stabilizing groups. In particular,the polymer backbone can be devoid of monomers that contain acidicfunctional groups. In this example, the reactive polyurethane dispersioncan include ionic stabilizing groups in the capping units, but not onthe polymer backbone. In a specific example, the polymer backbone can bedevoid of carboxylate and sulfonate groups.

In further examples, the reactive polyurethane dispersion can have aNCO/OH ratio of 1.2 to 10. In another example, the reactive polyurethanedispersion can have a NCO/OH ratio of 2 to 3. As used herein, “NCO/OHratio” refers to the mole ratio of NCO groups to OH groups in themonomers that react to form the polymer backbone.

In still further examples, the reactive polyurethane dispersion can havea double bond density of 1.5 to 10. In other examples, the reactivepolyurethane dispersion can have a double bond density of 2 to 10, 3 to10, or 4 to 10. As used herein, “double bond density” refers to thenumber of millimoles of double bonds in 1 g of the polyurethane polymerby dry weight.

The reactive polyurethane dispersions described herein can have an acidnumber from 20 to 100. In further examples, the reactive polyurethanedispersion can have an acid number from 25 to 80, from 30 to 60, or from35 to 50. As used herein, “acid number” refers to the number ofmilligrams of potassium hydroxide required to neutralize one gram of thepolyurethane dispersion, by solid weight.

In some examples, the reactive polyurethane dispersions can have aminimum film-forming temperature from −50° C. to 80° C. In furtherexamples, the reactive polyurethane dispersions can have a minimumfilm-forming temperature from −30° C. to 60° C. or from −25° C. to 50°C.

The molecular weight of the polyurethane can be also be controlled. Insome examples, the reactive polyurethane dispersion can have a weightaverage molecular weight M_(w) from 1,000 to 50,000. In furtherexamples, the reactive polyurethane dispersion can have a M_(w) from2,000 to 25,000 or from 3,000 to 10,000.

The reactive polyurethane dispersions can be incorporated intoUV-curable ink compositions. In some examples, a UV-curable inkcomposition can include a colorant, a photoinitiator, and a reactivepolyurethane dispersion as described herein. In one example, thereactive polyurethane dispersion can include a polymer strand that has apolymer backbone terminating at a first capping unit and a secondcapping unit at two ends of the polymer backbone. The polymer backbonecan include polymerized monomers such as a reactive diol and adiisocyanate. The reactive diol can be selected from anacrylate-containing diol, a methacrylate-containing diol, anacrylamide-containing diol, a methacrylamide-containing diol, orcombination thereof. The first capping unit can be anacrylamide-containing or methacrylamide-containing monoalcohol reactedwith an isocyanate group of the diisocyanate. The second capping unitcan be an ionic stabilizing group.

In some examples, the UV-curable ink composition can be a basic aqueousink. In one example, the UV-curable ink composition can have a pH of 7.0to 11.5. In further examples, the UV-curable ink composition can have apH of 7.5 to 10.5 or 8.0 to 9.0. The reactive polyurethane dispersion inthe UV-curable ink composition can be pH stable at these conditions,meaning that the pH of the UV-curable ink composition stays nearlyconstant over time. In one example, the pH of the UV-curable inkcomposition can be sufficiently stable that the pH does not decrease bymore than 1.0 when the UV-curable ink composition is exposed toaccelerated shelf-life (ASL) at 50° C. in open air for 1 week. Each weekof ASL is assumed to correspond to six months of shelf-life under normalstorage conditions. In a further example, the pH-stability of theUV-curable ink composition may be improved by using a polymer backbonethat is devoid of ionic stabilizing groups in the reactive polyurethanedispersion.

The UV-curable ink composition can also include a photoinitiator. Thephotoinitiator can be a material that generates radicals duringUV-curing. Radicals produced by the photoinitiator upon exposure to UVradiation can initiate bonding between the reactive groups in thereactive polyurethane dispersion. In some examples, the photoinitiatorcan be a type I photoinitiator, which is a unimolecular photoinitiatorthat generates radicals upon absorption of UV radiation. In furtherexamples, the photoinitiator can be a type II photoinitiator, which canbe used together with a synergist to generate radicals by hydrogenabstraction from the synergist. Non-limiting examples of photoinitiatorsthat can be used in the UV-curable ink composition can include1-hydroxy-cyclohexylphenylketone, benzophenone,2,4,6-trimethylbenzo-phenone, 4-methylbenzophenone,diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6trimethylbenzoyl)phosphine oxide,2-hydroxy-2-methyl-1-phenyl-1-propanone, benzyl-dimethyl ketal,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, orcombinations thereof. Non-limiting examples of additional photoinitiators include alpha amino ketone UV photo initiators such as Ciba®Irgacure® 907, Ciba® Irgacure® 369, and Ciba® Irgacure® 379; bisacylphosphine oxide (BAPO) UV photo initiators such as Ciba® Irgacure®819, Ciba® Darocur® 4265, and Ciba® Darocur® TPO; alpha hydroxy ketoneUV photo initiators such as Ciba® Irgacure® 184 and Ciba® Darocur® 1173;including photo initiators with or without sensitizers such as Ciba®Darocur® ITX (2-isopropyl thioxanthone). In some examples, thephotoinitiator can be water-soluble or water-dispersible.

In a particular example, the photoinitiator can have the generalformula:

where R₁ to R₄ are independently a hydrogen atom, an unsubstitutedalkyl, a substituted alkyl, an unsubstituted alkenyl, a substitutedalkenyl, an unsubstituted aryl, a substituted aryl, an unsubstitutedaralkyl, a substituted aralkyl, a halogen atom, —NO₂, —O—R_(d),—CO—R_(d), —CO—O—R_(d), —O—CO—R_(d), —CO—NR_(d)R_(e), —NR_(d)R_(e),—NR_(d)—CO—R_(e), —NR_(d)—CO—O—R_(e), —NR_(d)—CO—NR_(e)R_(f), —SR_(d),—SO—R_(d), —SO₂—R_(d), —SO₂—O—R_(d), —SO₂NR_(d)R_(e), or aperfluoroalkyl group. R_(d), R_(e), and R_(f) are independently ahydrogen atom, an unsubstituted alkyl, a substituted alkyl, anunsubstituted alkenyl, a substituted alkenyl, an unsubstituted aryl, asubstituted aryl, an unsubstituted aralkyl, or a substituted aralkyl. Xis selected from —O—, —S—, —NH—, and —NR—, where R is selected from CH₃,CH₂CH₃, and CH₂CH₂CH₃. R₅ can be an organic group that includes apolyether chain.

In another particular example, the photoinitiator can have the generalformula:

where R₁ to R₅ are independently a hydrogen atom, an unsubstitutedalkyl, a substituted alkyl, an unsubstituted alkenyl, a substitutedalkenyl, an unsubstituted aryl, a substituted aryl, an unsubstitutedaralkyl, a substituted aralkyl, a halogen atom, —NO₂, —O—R_(d),—CO—R_(d), —CO—O—R_(d), —O—CO—R_(d), —CO—NR_(d)R_(e), —NR_(d)R_(e),—NR_(d)—CO—R_(e), —NR_(d)—CO—O—R_(e), —NR_(d)—CO—NR_(e)R_(f), —SR_(d),—SO—R_(d), —SO₂—R_(d), —SO₂—O—R_(d), —SO₂NR_(d)R_(e), or aperfluoroalkyl group. R_(d), R_(e), and R_(f) are independently ahydrogen atom, an unsubstituted alkyl, a substituted alkyl, anunsubstituted alkenyl, a substituted alkenyl, an unsubstituted aryl, asubstituted aryl, an unsubstituted aralkyl, or a substituted aralkyl. Xis selected from —O—, —S—, —NH—, and —NR—, where R is selected from CH₃,CH₂CH₃, and CH₂CH₂CH₃. Y is selected from a bond, (CH₂)_(q), andO(CH₂)_(q), where q is any integer from 1 to 100. R₆ can be an organicgroup that includes a polyether chain.

Synergists can often be amines or alcohols. Non-limiting examples ofsynergists that can be used can include trimethylamine, triethanolamine,methyldiethanolamine, phenyldiethanolamine,N,N,N′,N′-tetra(hydroxylethyl)ethylenediamine, dimethylaminoethylacrylate, dimethylaminoethyl methacrylate, ethyl dimethylaminobenzoate,or a combination thereof. In some examples, the synergist can bewater-soluble or water-dispersible.

In a particular example, the synergist can have a general formulaselected from:

where R₁ to R₄ are independently a hydrogen atom, an unsubstitutedalkyl, a substituted alkyl, an unsubstituted alkenyl, a substitutedalkenyl, an unsubstituted aryl, a substituted aryl, an unsubstitutedaralkyl, a substituted aralkyl, a halogen atom, —NO₂, —O—R_(d),—CO—R_(d), —CO—O—R_(d), —O—CO—R_(d), —CO—NR_(d)R_(e), —NR_(d)R_(e),—NR_(d)—CO—R_(e), —NR_(d)—CO—O—R_(e), —NR_(d)—CO—NR_(e)R_(f), —SR_(d),—SO—R_(d), —SO₂—R_(d), —SO₂—O—R_(d), —SO₂NR_(d)R_(e), or aperfluoroalkyl group. R_(d), R_(e), and R_(f) are independently ahydrogen atom, an unsubstituted alkyl, a substituted alkyl, anunsubstituted alkenyl, a substituted alkenyl, an unsubstituted aryl, asubstituted aryl, an unsubstituted aralkyl, or a substituted aralkyl.The numbers m, n, and p are independently any integer from 0 to 200,provided that the sum of m, n, and p is at least 5. Y is selected from abond, (CH₂)_(q), and O(CH₂)_(q), where q is any integer from 1 to 100.

The UV-curable ink composition can be curable UV radiation, such asradiation produced by UV light emitting diodes (LEDs), UV fluorescentlamps, UV lasers, UV incandescent lamps, sunlight, and other UVradiation sources.

The colorant in the UV-curable ink composition can be a pigment, a dye,or a combination thereof. In some examples, the colorant can be presentin an amount from 0.5 wt % to 10 wt % in the UV-curable ink composition.In one example, the colorant can be present in an amount from 1 wt % to5 wt %. In another example, the colorant can be present in an amountfrom 5 wt % to 10 wt %.

In some examples, the colorant can be a dye. The dye can be nonionic,cationic, anionic, or a mixture of nonionic, cationic, and/or anionicdyes. Specific examples of dyes that can be used include, but are notlimited to, Sulforhodamine B, Acid Blue 113, Acid Blue 29, Acid Red 4,Rose Bengal, Acid Yellow 17, Acid Yellow 29, Acid Yellow 42, AcridineYellow G, Acid Yellow 23, Acid Blue 9, Nitro Blue Tetrazolium ChlorideMonohydrate or Nitro BT, Rhodamine 6G, Rhodamine 123, Rhodamine B,Rhodamine B Isocyanate, Safranine O, Azure B, and Azure B Eosinate,which are available from Sigma-Aldrich Chemical Company (St. Louis,Mo.). Examples of anionic, water-soluble dyes include, but are notlimited to, Direct Yellow 132, Direct Blue 199, Magenta 377 (availablefrom Ilford AG, Switzerland), alone or together with Acid Red 52.Examples of water-insoluble dyes include azo, xanthene, methine,polymethine, and anthraquinone dyes. Specific examples ofwater-insoluble dyes include Orasol® Blue GN, Orasol® Pink, and Orasol®Yellow dyes available from Ciba-Geigy Corp. Black dyes may include, butare not limited to, Direct Black 154, Direct Black 168, Fast Black 2,Direct Black 171, Direct Black 19, Acid Black 1, Acid Black 191, MobayBlack SP, and Acid Black 2.

In other examples, the colorant can be a pigment. The pigment can beself-dispersed with a polymer, oligomer, or small molecule; or can bedispersed with a separate dispersant. Suitable pigments include, but arenot limited to, the following pigments available from BASF: Paliogen®Orange, Heliogen® Blue L 6901F, Heliogen® Blue NBD 7010, Heliogen® BlueK 7090, Heliogen® Blue L 7101 F, Paliogen® Blue L 6470, Heliogen® GreenK 8683, and Heliogen® Green L 9140. The following black pigments areavailable from Cabot: Monarch® 1400, Monarch® 1300, Monarch® 1100,Monarch® 1000, Monarch® 900, Monarch® 880, Monarch® 800, and Monarch®700. The following pigments are available from CIBA: Chromophtal® Yellow3G, Chromophtal® Yellow GR, Chromophtal® Yellow 8G, Igrazin® Yellow 5GT,Igralite® Rubine 4BL, Monastral® Magenta, Monastral® Scarlet, Monastral®Violet R, Monastral® Red B, and Monastral® Violet Maroon B. Thefollowing pigments are available from Degussa: Printex® U, Printex® V,Printex® 140U, Printex® 140V, Color Black FW 200, Color Black FW 2,Color Black FW 2V, Color Black FW 1, Color Black FW 18, Color Black S160, Color Black S 170, Special Black 6, Special Black 5, Special Black4A, and Special Black 4. The following pigment is available from DuPont:Tipure® R-101. The following pigments are available from Heubach:Dalamar® Yellow YT-858-D and Heucophthal Blue G XBT-583D. The followingpigments are available from Clariant: Permanent Yellow GR, PermanentYellow G, Permanent Yellow DHG, Permanent Yellow NCG-71, PermanentYellow GG, Hansa Yellow RA, Hansa Brilliant Yellow 5GX-02, HansaYellow-X, Novoperm® Yellow HR, Novoperm® Yellow FGL, Hansa BrilliantYellow 10GX, Permanent Yellow G3R-01, Hostaperm® Yellow H4G, Hostaperm®Yellow H3G, Hostaperm® Orange GR, Hostaperm® Scarlet GO, and PermanentRubine F6B. The following pigments are available from Mobay: Quindo®Magenta, Indofast® Brilliant Scarlet, Quindo® Red R6700, Quindo® RedR6713, and Indofast® Violet. The following pigments are available fromSun Chemical: L74-1357 Yellow, L75-1331 Yellow, and L75-2577 Yellow. Thefollowing pigments are available from Columbian: Raven® 7000, Raven®5750, Raven® 5250, Raven® 5000, and Raven® 3500. The following pigmentis available from Sun Chemical: LHD9303 Black. Any other pigment and/ordye can be used that is useful in modifying the color of the UV-curableink composition. Additionally, the colorant can include a white pigmentsuch as titanium dioxide, or other inorganic pigments such as zinc oxideand iron oxide.

The components of the UV-curable ink composition can be selected to givethe composition good ink jetting performance. Besides the colorant,photoinitiator, and reactive polyurethane dispersion, the UV-curable inkcomposition can also include a liquid vehicle. Liquid vehicleformulations that can be used in the UV-curable ink composition caninclude water and one or more co-solvents present in total at from 1 wt% to 50 wt %, depending on the jetting architecture. Further, one ormore non-ionic, cationic, and/or anionic surfactant can be present,ranging from 0.01 wt % to 20 wt % (if present). In one example, thesurfactant can be present in an amount from 5 wt % to 20 wt %. Theliquid vehicle can also include dispersants in an amount from 5 wt % to20 wt %. The balance of the formulation can be purified water, or othervehicle components such as biocides, viscosity modifiers, materials forpH adjustment, sequestering agents, preservatives, and the like. In oneexample, the liquid vehicle can be predominantly water.

Classes of co-solvents that can be used can include organic co-solventsincluding aliphatic alcohols, aromatic alcohols, diols, glycol ethers,polyglycol ethers, caprolactams, formamides, acetamides, and long chainalcohols. Examples of such compounds include primary aliphatic alcohols,secondary aliphatic alcohols, 1,2-alcohols, 1,3-alcohols, 1,5-alcohols,ethylene glycol alkyl ethers, propylene glycol alkyl ethers, higherhomologs (C₆-C₁₂) of polyethylene glycol alkyl ethers, N-alkylcaprolactams, unsubstituted caprolactams, both substituted andunsubstituted formamides, both substituted and unsubstituted acetamides,and the like. Specific examples of solvents that can be used include,but are not limited to, 2-pyrrolidinone, N-methylpyrrolidone,2-hydroxyethyl-2-pyrrolidone, 2-methyl-1,3-propanediol, tetraethyleneglycol, 1,6-hexanediol, 1,5-hexanediol and 1,5-pentanediol.

In some examples, the UV-curable ink composition can include one or morecurable solvents that can participate in UV-curing with the reactivepolyurethane dispersion. Non-limiting examples of curable solvents thatcan be used can include hydroyethylacrylamide, N-vinyl imidazole,N-vinyl-N-methylacetamide, N-vinyl caprolactam, diethyleneglycolvinylether, tetraethyleneglycol vinylether, diacetone acrylamide, sodium2-acrylamide-2-methyl-1-propane sulfonate, and others.

One or more surfactants can also be used, such as alkyl polyethyleneoxides, alkyl phenyl polyethylene oxides, polyethylene oxide blockcopolymers, acetylenic polyethylene oxides, polyethylene oxide(di)esters, polyethylene oxide amines, protonated polyethylene oxideamines, protonated polyethylene oxide amides, dimethicone copolyols,substituted amine oxides, and the like. The amount of surfactant addedto the composition may range from 0.01 wt % to 20 wt %. Suitablesurfactants can include, but are not limited to, liponic esters such asTergitol™ 15-S-12, Tergitol™ 15-S-7 available from Dow Chemical Company,LEG-1 and LEG-7; Triton™ X-100; Triton™ X-405 available from DowChemical Company; LEG-1, and sodium dodecylsulfate.

Various other additives can be employed to optimize the properties ofthe UV-curable ink composition for specific applications. Examples ofthese additives are those added to inhibit the growth of harmfulmicroorganisms. These additives may be biocides, fungicides, and othermicrobial agents. Examples of suitable microbial agents include, but arenot limited to, NUOSEPT® (Nudex, Inc.), UCARCIDE™ (Union carbide Corp.),VANCIDE® (R.T. Vanderbilt Co.), PROXEL® (ICI America), or a combinationthereof.

Sequestering agents, such as EDTA (ethylene diamine tetra acetic acid),may be included to eliminate the deleterious effects of heavy metalimpurities, and buffer solutions may be used to control the pH of theink. From 0.01 wt % to 2 wt %, for example, can be used if present.Viscosity modifiers and buffers may also be present, as well as otheradditives to modify properties of the ink as desired. Such additives canbe present at from 0.01 wt % to 20 wt % if present.

The UV-curable ink composition can be used to print on a broad selectionof substrates including untreated plastics, flexible as well as rigid,porous substrates such as paper, cardboard, foam board, textile, andothers. The composition can have a good adhesion on a variety ofsubstrates. The composition can also have a good viscosity, enablinggood printing performance in inkjet printing. In some examples, theUV-curable ink composition can be formulated for thermal inkjetprinting.

The reactive polyurethane dispersions described herein can be formed byreacting appropriate monomers in an appropriate reaction sequence toform the polymer backbone and the capping units. In one example, amethod of making the reactive polyurethane dispersion can includereacting a diisocyanate with a reactive diol to form a firstpre-polymer. The reactive diol can be an acrylate-containing diol, amethacrylate-containing diol, an acrylamide-containing diol, amethacrylamide-containing diol, or a combination thereof. The firstpre-polymer can then be reacted with an acrylamide-containing ormethacrylamide-containing monoalcohol to form a second pre-polymer. Thesecond pre-polymer can be reacted with an acid-containing amine to forma polymer strand. The polymer strand can then be dispersed in water toform the reactive polyurethane dispersion.

In one example, a polymer strand of the reactive polyurethane dispersioncan be formed by following the reaction scheme shown in FIG. 1. Adiisocyanate 1 and reactive diol 2 can react to form a first pre-polymer3. In these steps, R₂ is an organic group and R₃ is an organic groupcontaining an acrylate, methacrylate, acrylamide, or methacrylamidefunctional group. In a certain example, the diisocyanate and reactivediol can be reacted with excess diisocyanate so that each polymer strandis likely to have a polymerized diisocyanate at each end. Thus, thefirst pre-polymer can have an unreacted isocyanate group available ateach end.

The first pre-polymer 3 can react with an acrylamide-containing ormethacrylamide-containing monoalcohol 4 to form a second pre-polymer 5.R₁ represents an organic group including an acrylamide or methacrylamidegroup. The acrylamide-containing or methacrylamide-containingmonoalcohol can polymerize with one of the isocyanate groups at one endof the first pre-polymer. Specifically, the oxygen atom of the hydroxylgroup of the monoalcohol can bond to the carbon atom of the isocyanategroup. The hydrogen atom of the hydroxyl group becomes bonded to thenitrogen atom in the isocyanate group when this reaction occurs. Thus,one end of the first pre-polymer can be capped with anacrylamide-containing or methacrylamide-containing capping unit to formthe second pre-polymer.

The second pre-polymer 5 can react with an acid-containing amine 6 suchas an amino acid or taurine to form the final polymer strand 7. R₄represents an organic group including an acidic group. R₅ representshydrogen or an additional organic group. The nitrogen atom of theacid-containing amine can bond to the carbon atom of the isocyanategroup. The hydrogen atom of the amine group becomes bonded to thenitrogen atom in the isocyanate group when this reaction occurs. Thus,the remaining end of the pre-polymer can be capped with anacid-containing amine.

FIG. 2 is a flowchart of another example of a method 200 of making areactive polyurethane dispersion. The method includes reacting 210 adiisocyanate with a reactive diol selected from an acrylate-containingdiol, a methacrylate-containing diol, an acrylamide-containing diol, amethacrylamide-containing diol, or combination thereof, to form a firstpre-polymer; reacting 220 the first pre-polymer with anacrylamide-containing or methacrylamide-containing monoalcohol to form asecond pre-polymer; reacting 230 the second pre-polymer with anacid-containing amine to form a polymer strand; and dispersing 240 thepolymer strand in water to form the reactive polyurethane dispersion.

In another example, a method of making a UV-curable ink composition caninclude making a reactive polyurethane dispersion as described above,and then adding a colorant and a photoinitiator to the reactivepolyurethane dispersion to form the UV-curable ink composition. Otheringredients of the UV-curable ink composition can also be added asdescribed above.

It is to be understood that this disclosure is not limited to theparticular process steps and materials disclosed herein because suchprocess steps and materials may vary somewhat. It is also to beunderstood that the terminology used herein is used for the purpose ofdescribing particular examples only. The terms are not intended to belimiting because the scope of the present disclosure is intended to belimited only by the appended claims and equivalents thereof.

It is noted that, as used in this specification and the appended claims,the singular forms “a,” “an,” and “the” include plural referents unlessthe context clearly dictates otherwise.

As used herein, “UV-curable” refers to compositions that can be cured byexposure to ultraviolet light from any UV source such as a mercury vaporlamp, UV LED source, or the like. Mercury vapor lamps emit highintensity light at wavelengths from 240 nm to 270 nm and 350 nm to 380nm. “LED curable” refers to compositions that can be cured either byultraviolet light from an ultraviolet LED. Ultraviolet LEDs emit lightat specific wavelengths. For example, ultraviolet LEDs are available at365 nm and 395 nm wavelengths, among others.

As used herein, “liquid vehicle” or “ink vehicle” refers to a liquidfluid in which colorant is placed to form an ink. A wide variety of inkvehicles may be used with the systems and methods of the presentdisclosure. Such ink vehicles may include a mixture of a variety ofdifferent agents, including, surfactants, solvents, co-solvents,anti-kogation agents, buffers, biocides, sequestering agents, viscositymodifiers, surface-active agents, water, etc.

As used herein, “colorant” can include dyes and/or pigments.

As used herein, “dye” refers to compounds or molecules that absorbelectromagnetic radiation or certain wavelengths thereof. Dyes canimpart a visible color to an ink if the dyes absorb wavelengths in thevisible spectrum.

As used herein, “pigment” generally includes pigment colorants, magneticparticles, aluminas, silicas, and/or other ceramics, organo-metallics orother opaque particles, whether or not such particulates impart color.Thus, though the present description primarily exemplifies the use ofpigment colorants, the term “pigment” can be used more generally todescribe not only pigment colorants, but other pigments such asorganometallics, ferrites, ceramics, etc. In one specific example,however, the pigment is a pigment colorant.

As used herein, “ink-jetting” or “jetting” refers to compositions thatare ejected from jetting architecture, such as ink-jet architecture.Ink-jet architecture can include thermal or piezo architecture.Additionally, such architecture can be configured to print varying dropsizes such as less than 10 picoliters, less than 20 picoliters, lessthan 30 picoliters, less than 40 picoliters, less than 50 picoliters,etc.

As used herein, the term “substantial” or “substantially” when used inreference to a quantity or amount of a material, or a specificcharacteristic thereof, refers to an amount that is sufficient toprovide an effect that the material or characteristic was intended toprovide. The exact degree of deviation allowable may in some casesdepend on the specific context.

As used herein, the term “about” is used to provide flexibility to anumerical range endpoint by providing that a given value may be “alittle above” or “a little below” the endpoint. The degree offlexibility of this term can be dictated by the particular variable anddetermined based on the associated description herein.

As used herein, a plurality of items, structural elements, compositionalelements, and/or materials may be presented in a common list forconvenience. However, these lists should be construed as though eachmember of the list is individually identified as a separate and uniquemember. Thus, no individual member of such list should be construed as ade facto equivalent of any other member of the same list solely based ontheir presentation in a common group without indications to thecontrary.

Concentrations, amounts, and other numerical data may be expressed orpresented herein in a range format. It is to be understood that such arange format is used merely for convenience and brevity and thus shouldbe interpreted flexibly to include not only the numerical valuesexplicitly recited as the limits of the range, but also to includeindividual numerical values or sub-ranges encompassed within that rangeas if each numerical value and sub-range is explicitly recited. As anillustration, a numerical range of “about 1 wt % to about 5 wt %” shouldbe interpreted to include not only the explicitly recited values ofabout 1 wt % to about 5 wt %, but also include individual values andsub-ranges within the indicated range. Thus, included in this numericalrange are individual values such as 2, 3.5, and 4 and sub-ranges such asfrom 1-3, from 2-4, and from 3-5, etc. This same principle applies toranges reciting only one numerical value. Furthermore, such aninterpretation should apply regardless of the breadth of the range orthe characteristics being described.

EXAMPLES

The following illustrates several examples of the present disclosure.However, it is to be understood that the following are only illustrativeof the application of the principles of the present disclosure. Numerousmodifications and alternative compositions, methods, and systems may bedevised without departing from the spirit and scope of the presentdisclosure. The appended claims are intended to cover such modificationsand arrangements.

Example 1—Synthesis of PUD 10

A reactive polyurethane dispersion (PUD 10) was synthesized using thefollowing procedure. 33.545 g of g of Bisphenol A glycerolate (1glycerol/phenol) diacrylate (BGDA) 0.335 g of 4-methoxyphenol (MEHQ),43.585 g of 4,4′-methylene dicyclohexyl diisocyanate (H12MDI), and 42 gof acetone were mixed in a 500 ml of 4-neck round bottom flask. Amechanical stirrer with glass rod and Teflon blade was attached. Acondenser was attached. The flask was immersed in a constant temperaturebath at 60° C. The system was kept under drying tube. 3 drops ofdibutyltin dilaurate (DBTDL) was added to initiate the polymerization.Polymerization was continued for 3 hrs at 60° C. A 0.5 g sample waswithdrawn for wt % NCO titration to confirm the reaction. The measuredNCO value was 10.35 wt %. Theoretical wt % NCO was 10.55 wt %. 15.939 gof HEAA (N-hydroxylethyl acrylamide, CAS #7646-67-5, purchased fromSigma Aldrich), 0.159 g of MEHQ, and 19 g of acetone were mixed in abeaker and added to the reactor over 30 sec. 9 g of acetone was used torinse off the residual monomers on the beaker and added to the reactor.The polymerization was continued 3 hours at 50° C. 0.5 g of pre-polymerwas withdrawn for final wt % NCO titration. The measured NCO value was2.45 wt %. The theoretical wt % NCO was 2.50 wt %. The polymerizationtemperature was reduced to 40° C. 6.931 g of taurine, 4.652 g of 50 wt %NaOH, and 34.653 g of deionized water are mixed in a beaker untiltaurine is completely dissolved. Taurine solution was added to thepre-polymer solution at 40° C. with vigorous stirring over 1-3 mins. Thesolution became viscous and slight hazy. Stirring was continued for 30mins at 40° C. The mixture became clear and viscous after 15-20 mins at40° C. 197.381 g of cold deionized water was added to polymer mixture in4-neck round bottom flask over 1-3 mins with good agitation to form PUDdispersion. The agitation was continued for 60 mins at 40° C. The PUDdispersion was filtered through 400 mesh stainless sieve. Acetone wasremoved with rotorvap at 50° C. (added 2 drops (20 mg) BYK-011de-foaming agent if there was excessive foaming). The final PUDdispersion was filtered through fiber glass filter paper. Particle sizemeasured by Malvern Zetasizer was 32.6 nm. The pH of the dispersion was7.5. Solid content was 29.08 wt %. This PUD showed less than 0.4 unit pHdrop after 1 week ASL.

Example 2—Synthesis of PUD 19

A reactive polyurethane dispersion (PUD 19) was synthesized using thefollowing procedure. 38.884 g of g of BGDA, 0.389 g of MEHQ, 42.103 g ofH12MDI, and 42 g of acetone were mixed in a 500 ml of 4-neck roundbottom flask. A mechanical stirrer with glass rod and Teflon blade wasattached. A condenser was attached. The flask was immersed in a constanttemperature bath at 60° C. The system was kept under drying tube. 3drops of DBTDL was added to initiate the polymerization. Polymerizationwas continued for 3 hrs at 60° C. A 0.5 g sample was withdrawn for wt %NCO titration to confirm the reaction. The measured NCO value was 7.6 wt%. Theoretical wt % NCO was 8.32 wt %. 12.318 g of HEAA (N-hydroxylethylacrylamide, CAS #7646-67-5, purchased from Sigma Aldrich), 0.159 g ofMEHQ, and 19 g of acetone were mixed in a beaker and added to thereactor over 30 sec. 9 g of acetone was used to rinse off the residualmonomers on the beaker and added to the reactor. The polymerization wascontinued 3 hours at 50° C. 0.5 g of pre-polymer was withdrawn for finalwt % NCO titration. The measured NCO value was 2.41 wt %. Thetheoretical wt % NCO was 2.41 wt %. The polymerization temperature wasreduced to 40° C. 6.695 g of taurine, 4.494 g of 50 wt % NaOH, and33.474 g of deionized water are mixed in a beaker until taurine iscompletely dissolved. Taurine solution was added to the pre-polymersolution at 40° C. with vigorous stirring over 1-3 mins. The solutionbecame viscous and slight hazy. Stirring continued for 30 mins at 40° C.The mixture became clear and viscous after 15-20 mins at 40° C. 194.649g of cold deionized water was added to the polymer mixture in 4-neckround bottom flask over 1-3 mins with good agitation to form PUDdispersion. The agitation was continued for 60 mins at 40° C. The PUDdispersion was filtered through 400 mesh stainless sieve. Acetone wasremoved with rotorvap at 50° C. (adding 2 drops (20 mg) BYK-011de-foaming agent if there was excessive foaming). The final PUDdispersion was filtered through fiber glass filter paper. Particle sizemeasured by Malvern Zetasizer was 26.8 nm. The pH of the dispersion was6.0. Solid content was 30.04 wt %. This PUD showed less than 0.4 unit pHdrop after 1 week ASL.

Example 3—Synthesis of PUD 13

A reactive polyurethane dispersion (PUD 13) was synthesized using thefollowing procedure. 33.732 g of g of BGDA, 0.337 g of MEHQ, 40.176 g ofH12MDI, 3.095 g of IPDI and 42 g of acetone were mixed in a 500 ml of4-neck round bottom flask. A mechanical stirrer with glass rod andTeflon blade was attached. A condenser was attached. The flask wasimmersed in a constant temperature bath at 60° C. The system was keptunder drying tube. 3 drops of DBTDL was added to initiate thepolymerization. Polymerization was continued for 3 hrs at 60° C. A 0.5 gsample was withdrawn for wt % NCO titration to confirm the reaction. Themeasured NCO value was 10.32 wt %. Theoretical wt % NCO was 10.63 wt %.16.028 g of HEAA (N-hydroxylethyl acrylamide, CAS #7646-67-5, purchasedfrom Sigma Aldrich), 0.160 g of MEHQ, and 19 g of acetone were mixed ina beaker and added to the reactor over 30 sec. 9 g of acetone was usedto rinse off the residual monomers on the beaker and added to thereactor. The polymerization was continued 3 hours at 50° C. 0.5 g ofpre-polymer was withdrawn for final wt % NCO titration. The measured NCOvalue was 2.49 wt %. The theoretical wt % NCO was 2.51 wt %. Thepolymerization temperature was reduced to 40° C. 6.969 g of taurine,4.678 g of 50 wt % NaOH, and 34.846 g of deionized water are mixed in abeaker until taurine is completely dissolved. Taurine solution was addedto the pre-polymer solution at 40° C. with vigorous stirring over 1-3mins. The solution became viscous and slight hazy. Stirring continuedfor 30 mins at 40° C. The mixture became clear and viscous after 15-20mins at 40° C. 197.314 g of cold deionized water was added to thepolymer mixture in 4-neck round bottom flask over 1-3 mins with goodagitation to form PUD dispersion. The agitation was continued for 60mins at 40° C. The PUD dispersion was filtered through 400 meshstainless sieve. Acetone was removed with rotorvap at 50° C. (adding 2drops (20 mg) BYK-011 de-foaming agent if there was excessive foaming).The final PUD dispersion was filtered through fiber glass filter paper.Particle size measured by Malvern Zetasizer was 25.5 nm. The pH of thedispersion was 7.4. Solid content was 30.0 wt %. This PUD showed lessthan 0.4 unit pH drop after 1 week ASL.

Example 4—Compositions of Additional PUDs

A series of the reactive polyurethane dispersions of Examples 1-3, aswell as several additional reactive polyurethane dispersions weresynthesized using procedures similar to the procedures described above.The compositions of the dispersions are shown in Table 1.

TABLE 1 IPDI H12MDI BGDA Taurine HEAA PUD # (wt %) (wt %) (wt %) (wt %)(wt %) 1 45.05 27.74 10.74 16.47 2 40.99 29.79 11.54 17.69 3 45.05 27.7410.74 16.47 4 40.99 29.79 11.54 17.69 5 45.11 27.78 8.97 18.15 6 45.1827.82 7.18 19.83 7 41.05 29.83 9.63 19.49 8 41.11 29.88 7.72 21.29 943.53 33.5 8.65 14.33 10 43.59 33.55 6.93 15.94 11 39.5 35.88 9.27 15.3512 39.56 35.94 7.43 17.08 13 3.1 40.18 33.73 6.97 16.03 14 6.22 36.7333.92 7.07 16.12 15 9.39 33.24 34.11 7.05 16.21 16 12.59 29.72 34.317.09 16.3 17 40.56 43.7 11.29 4.45 18 42.05 38.83 8.36 10.76 19 42.138.88 6.70 12.32 20 38.069 41.5 8.93 11.5 21 38.124 41.56 7.16 13.16 2238.16 52.86 7.58 1.4

In Table 1, PUD # is the number designating the reactive polyurethanedispersion; IPDI is the weight percent of isophorone diisocyanate usedto form the polyurethane dispersion, based on the total weight ofmonomers reacted to form the polyurethane dispersion; H12MDI is theweight percent of 4,4′-Methylene dicyclohexyl diisocyanate; BGDA is theweight percent of Bisphenol A glycerolate (1 glycerol/phenol)diacrylate; Taurine is the weight percent of taurine; and HEAA is theweight percent of N-hydroxyethyl acrylamide.

Several properties of these reactive polyurethane dispersions are shownin Table 2.

TABLE 2 Particle size Acid Double bond NCO/OH PUD # (nm) Number densitypH ratio 1 19.01 48.2 2.6 7.5 3 2 13.91 51.7 2.8 7.5 3 3 15.7 48.2 2.67.0 3 4 25.09 51.7 2.8 7.5 3 5 18.28 40.2 2.7 6.0 3 6 24.42 32.2 2.9 6.53 7 14.52 43.2 2.9 5.5 3 8 17.63 34.6 3.1 5.5 3 9 17.33 38.8 2.6 7.5 2.410 32.55 31.1 2.8 7.5 2.4 11 25.63 41.5 2.8 7.5 2.4 12 17.31 33.3 3 7.52.4 13 25.52 31.2 2.8 7.5 2.4 14 23.25 31.4 2.8 7.0 2.4 15 19.94 31.62.8 7.5 2.4 16 19.26 31.8 2.8 7.5 2.4 17 15.71 50.6 2.2 6.0 2.2 18 20.8737.5 2.5 7.5 2 19 26.75 30 2.7 5.5 2 20 68.23 40 2.7 6.0 2 21 17.3632.10 2.9 6.0 2 22 38.53 34 2.3 5.5 1.33

In Table 2, particle size refers to the average diameter of theparticles in nanometers. Acid number, double bond density, and NCO/OHratio are as defined above.

Example 5—UV-Curable Ink Compositions

UV-curable ink compositions were formed using the reactive polyurethanedispersions shown in Table 1. The UV-curable ink compositions had thefollowing composition: 10.00 wt % reactive polyurethane dispersion; 0.80wt % Surfynol® CT-211 (Air Products); 0.50 wt % DX-4000™ (Dynax); 0.50wt % sodium phenyl-(2,4,6-trimethylbenzoyl)phosphinate (TPA Na); 0.25 wt% 2-Methoxypolyethyleneglycol-9H-Thioxanthen-9-one (M-TX-PEG-550); 4.00wt % magenta pigment; balance water. Each ink was printed using aninkjet printer at a rate of 100 ft/min and cured under UV LED light at25 ft/min.

The ink films were subjected to the following tests: a) Eraser Rub: rubwith a pencil eraser 10 times with 250 g of weight applied; b) WindexRub: rub with Crockmeter Test Cloth and Windex® cleaning solution 5times with 250 g of weight applied; c) Wet Rub: rub once with CrockmeterTest Cloth and water with no applied weight; d) 70 vol % IPA Rub: rubwith Crockmeter Test Cloth and 70 vol % isopropyl alcohol with 250 g ofweight applied; e) Tape Adhesion: apply Scotch® tape and then remove; f)Sutherland® Rub Test: On a Sutherland® Rub Tester, heat to 350° F., rub10 times with 4 psi at speed 2. All of the rub tests except forSutherland® Rub Test are scored from 0.0 to 5.0 with 0.0 being the bestscore and 5.0 being the worst score. The Sutherland® Rub Test is scoredfrom 1.0 to 5.0 with 5.0 being the best score and 1.0 being the worstscore (notably numerically scored oppositely compared to the Sutherland®Rub Test). The durability results are reported in Table 3 below. Table 3also shows ASL stability and durability of magenta inks based on thesecurable acrylamide based PUDs. All of these acrylamide based curablePUDs have excellent pH stability and ASL particle size and viscositystability. Additionally, all of these magenta inks based on acrylamidecapped PUDs have excellent wet rub, Sutherland durability and generallygood tape adhesion. A majority of these magenta inks demonstratedgenerally good Eraser durability. Several magenta inks showed excellentIPA durability such as CPUD 247, CPUD 251 and CPUD 382.

TABLE 2 Optical Eraser Windex 70 vol Wet PUD # Density 75° Gloss Rub Rub% IPA Rub 1 1.71 84 2.5 5 5 3 2 1.8 84 4 5 5 5 3 1.75 84 2.5 5 5 2 4 1.884 4 5 5 4 5 1.64 83 3 0.5 3 0 6 1.49 80 2 2 2 0 7 1.6 79 3.5 5 5 0 81.48 78 4 4.5 5 0 9 1.76 84 3 4.5 4 0 10 1.44 79 3 0.5 0.5 0 11 1.68 792.5 5 4.5 0 12 1.76 80 2.5 5 4 0 13 1.42 75 3 0.5 1 0 14 1.4 78 3 2 3 015 1.42 78 3.5 2 3 0 16 1.49 80 3.5 3 3 0 17 1.46 78 3 2 4 0 18 1.32 713.5 0.5 3 0 19 1.25 69 2.5 0 2 0 20 1.37 78 3.5 4 4 0 21 1.42 79 3.5 3.52 0 22 1.35 71 3 0.5 2 0 % % % Tape Delta Change Change Change PUD #Adhesion Sutherland pH Viscosity Mv D95 1 3 2 0.25 5 12 8 2 5 1 0.35 6 76 3 2.5 3 0.48 8 7.7 5 4 5 1 0.42 6 3.6 7.5 5 3.5 5 0.59 4.3 10.2 11.8 60 4 0.41 13 19.3 15.8 7 5 5 0.80 56 83.3 104 8 5 3 0.81 58.3 81.7 120.69 1 5 0.35 6 10 7 10 0 5 0.47 7.7 14 12 11 0 5 0.25 3 6 8 12 0 5 0.3 7 99 13 0 5 0.19 10 21.2 21.5 14 2 4 0.39 5 −13.1 −7.4 15 5 5 0.79 0 10.111.4 16 3.5 5 0.45 4.8 10.1 18.3 17 3.5 5 0.76 −4.8 5.8 0.7 18 3.5 50.19 −3.4 4.8 1.8 19 0.5 5 0.13 7.7 8.1 5.8 20 4.5 3 0.52 −3.6 10.7 4.721 4 3 0.54 0 4.9 11.7 22 0 5 0.76 10 4.6 −1.3

While the present technology has been described with reference tocertain examples, those skilled in the art will appreciate that variousmodifications, changes, omissions, and substitutions can be made withoutdeparting from the spirit of the disclosure. It is intended, therefore,that the disclosure be limited only by the scope of the followingclaims.

What is claimed is:
 1. A reactive polyurethane dispersion, comprising apolymer strand comprising a polymer backbone having two terminating endscomprising a first capping unit at a first terminating end and a secondcapping unit at a second terminating end, wherein the polymer backbonecomprises polymerized monomers including: a reactive diol selected froman acrylate-containing diol, a methacrylate-containing diol, anacrylamide-containing diol, a methacrylamide-containing diol, orcombination thereof; and a diisocyanate, wherein the first capping unitis an acrylamide-containing monoalcohol or methacrylamide-containingmonoalcohol reacted with an isocyanate group of the diisocyanate;wherein the second capping unit is an ionic stabilizing group; andwherein the reactive polyurethane dispersion has a NCO/OH ratio of 1.2to
 10. 2. The reactive polyurethane dispersion of claim 1, wherein thepolymer backbone is devoid of ionic stabilizing groups.
 3. The reactivepolyurethane dispersion of claim 1, wherein the reactive polyurethanedispersion has an acid number of 20 to
 100. 4. The reactive polyurethanedispersion of claim 1, wherein the reactive polyurethane dispersion hasa double bond density of 1.5 to
 10. 5. The reactive polyurethanedispersion of claim 1, wherein the acrylamide-containing monoalcohol ormethacrylamide-containing monoalcohol is selected from:

or a combination thereof.
 6. The reactive polyurethane dispersion ofclaim 1, wherein the reactive diol is selected from:

or a combination thereof.
 7. The reactive polyurethane dispersion ofclaim 1, wherein the reactive polyurethane dispersion is devoid ofpolymer strands having capping units that include acrylate groups ormethacrylate groups.
 8. The reactive polyurethane dispersion of claim 1,wherein a majority of polymer strands in the reactive polyurethanedispersion have a first capping unit that is an acrylamide-containingmonoalcohol or methacrylamide-containing monoalcohol reacted with anisocyanate group of the diisocyanate and a second capping unit that isan ionic stabilizing group.
 9. A UV-curable ink composition, comprising:a colorant; a photoinitiator; and a reactive polyurethane dispersion,comprising a polymer strand comprising a polymer backbone having twoterminating ends comprising a first capping unit at a first terminatingend and a second capping unit at a second terminating end, wherein thepolymer backbone comprises polymerized monomers including: a reactivediol selected from an acrylate-containing diol, amethacrylate-containing diol, an acrylamide-containing diol, amethacrylamide-containing diol, or combination thereof, and adiisocyanate, wherein the first capping unit is an acrylamide-containingmonoalcohol or methacrylamide-containing monoalcohol reacted with anisocyanate group of the diisocyanate; and B wherein the second cappingunit is an ionic stabilizing group.
 10. The UV-curable ink compositionof claim 9, wherein the UV-curable ink composition has a pH of 7.0 to11.5.
 11. The UV-curable ink composition of claim 10, wherein the pHdoes not decrease by more than 1.0 when the UV-curable ink compositionis exposed to accelerated shelf-life (ASL) at 50° C. in open air for 1week.
 12. The UV-curable ink composition of claim 9, wherein the polymerbackbone is devoid of ionic stabilizing groups.
 13. A method of making areactive polyurethane dispersion, comprising: reacting a diisocyanatewith a reactive diol selected from an acrylate-containing diol, amethacrylate-containing diol, an acrylamide-containing diol, amethacrylamide-containing diol, or combination thereof, to form a firstpre-polymer; reacting the first pre-polymer with anacrylamide-containing monoalcohol or methacrylamide-containingmonoalcohol to form a second pre-polymer; reacting the secondpre-polymer with an acid-containing amine to form a polymer strand; anddispersing the polymer strand in water to form the reactive polyurethanehaving a NCO/OH ratio of 1.2 to
 10. 14. The method of claim 13, furthercomprising adding a colorant and a photoinitiator to the reactivepolyurethane dispersion to form a UV-curable ink composition.
 15. Areactive polyurethane dispersion, comprising a polymer strand comprisinga polymer backbone having two ends terminating at a first capping unitand a second capping unit, wherein the polymer backbone comprisespolymerized monomers including: a reactive diol selected from:

or a combination thereof; and a diisocyanate, wherein the first cappingunit is an acrylamide-containing monoalcohol ormethacrylamide-containing monoalcohol reacted with an isocyanate groupof the diisocyanate; and wherein the second capping unit is an ionicstabilizing group.
 16. The reactive polyurethane dispersion of claim 15,wherein the polymer backbone is devoid of ionic stabilizing groups. 17.The reactive polyurethane dispersion of claim 15, wherein the reactivepolyurethane dispersion has an acid number of 20 to 100, a double bonddensity of 1.5 to 10, or is devoid of polymer strands having cappingunits that include acrylate groups or methacrylate groups.
 18. Thereactive polyurethane dispersion of claim 15, wherein theacrylamide-containing monoalcohol or methacrylamide-containingmonoalcohol is selected from:

or a combination thereof.
 19. A method of making a reactive polyurethanedispersion, comprising: reacting a diisocyanate with a reactive diolselected from:

or a combination thereof, to form a first pre-polymer; reacting thefirst pre-polymer with an acrylamide-containing monoalcohol ormethacrylamide-containing monoalcohol to form a second pre-polymer;reacting the second pre-polymer with an acid-containing amine to form apolymer strand; and dispersing the polymer strand in water to form thereactive polyurethane.
 20. The method of claim 19, further comprisingadding a colorant and a photoinitiator to the reactive polyurethanedispersion to form a UV-curable ink composition.